Heat-resistant label applicable at high temperature

ABSTRACT

The present invention relates to compositions for heat-resistant labels that are attachable under high-temperature conditions of 300° C. to 1100° C., heat-resistant labels, products with the labels attached, and methods for producing the labels. The invention employs, as a sticking layer of heat resistant labels, a hardened coating film including a silicone resin (A) and at least one member selected from the group consisting of a polymetallocarbosilane resin, zinc powder, tin powder, and aluminum powder (B), thereby providing heat resistant labels that can be attached at high temperature conditions.

TECHNICAL FIELD

The present invention relates to compositions for heat-resistant labelsthat are attachable to high-temperature products (300° C. or higher),heat-resistant labels, products with the labels attached, and methodsfor producing the labels.

BACKGROUND OF THE INVENTION

In various industrial fields, such as food, machinery and chemicals, alabel on which symbols, letters, patterns, etc., have been printed,i.e., a patterned label, is attached to products or their packagingmaterials to control the production process. A typical example of suchprocess control is a system utilizing labels on which a bar-code isprinted. In a bar-code control system, data such as productionconditions, production managers, production period, destination, andproduct price are read from the bar-code label by a bar-code reader tocontrol production, sales, and distribution.

The bar-code labels that are currently in wide use are made by producinga resin or paper label having poor heat resistance, and then applying anadhesive made of acrylic resin or the like to it. However, because boththe label and the adhesive decompose and evaporate at temperatures of300° C. or higher, they cannot be used in industries requiringhigh-temperature processing, such as ceramics, metals, and the like.Japanese Patent No. 2614022 discloses heat-resistant labels but does notdisclose attaching the labels at such high temperatures. JapaneseUnexamined Patent Publication No. 2003-126911 discloses labels to besubjected to a heating process in which an aluminum coil is baked butdiscloses in Comparative Example 3 in the specification that theinformation on the label becomes unclear unless the attachmenttemperature is 150° C. or lower.

Therefore, in the metal mining industry, labels for product managementare attached to metal products after the melted and formed metal iscooled to a temperature (generally, near room temperature) in the rangein which the labels can be attached. The same applies to the ceramicsand glass industries, and other industries requiring high-temperatureprocessing.

DISCLOSURE OF THE INVENTION

However, labels that can be attached to high-temperature products allowproduct management to be started at an earlier stage in the productionprocess.

Accordingly, an object of the present invention is to provide aheat-resistant label attachable to high-temperature products.

Another object of the invention is to provide a composition for aheat-resistant label to produce the heat resistant label.

Still another object of the invention is to provide an article to whichthe heat-resistant label has been attached.

The inventors carried out extensive research to achieve theabove-mentioned objects in view of the problems of the prior art. As aresult, they found that heat-resistant labels having as a sticking layera hardened coating film made of a composition comprising a siliconeresin (A); at least one member selected from the group consisting of apolymetallocarbosilane resin, zinc powder, tin powder, and aluminumpowder (B); and a solvent (C) can be attached to high-temperatureproducts of 300° C. or higher. The inventors further found thatheat-resistant labels with an aluminum foil layer or tin foil layer onone side (adhering side) of a very high temperature-resistant support(e.g., stainless support, copper support) can be attached attemperatures of 670° C. to 1100° C., or 300° C. to 1100° C.,respectively, and the present invention has been accomplished based onthese findings.

The present invention thus relates to the following compositions,heat-resistant labels, products with heat-resistant labels attached, andmethods for producing the products.

-   Item 1. A composition for a heat-resistant label comprising a    silicone resin (A), at least one member selected from the group    consisting of a polymetallocarbosilane resin, zinc powder, tin    powder and aluminum powder (B), and a solvent (C).-   Item 2. A composition for a heat-resistant label according to item 1    comprising a silicone resin (A), a polymetallocarbosilane resin    (B-1), and a solvent (C).-   Item 3. A composition for a heat-resistant label according to item 1    or 2, wherein the weight ratio of the silicone resin (A): the    polymetallocarbosilane resin (B-1) is about 1:9 to about 9:1.-   Item 4. A composition for a heat-resistant label according to any    one of items 1 to 3, wherein the weight ratio of the silicone    resin (A) the polymetallocarbosilane resin (B-1) is about 7:3 to    about 2:8.-   Item 5. A composition for a heat-resistant label according to any    one of items 1 to 4, wherein the silicone resin (A) has a    weight-average molecular weight of about 1000 to about 5000000.-   Item 6. A composition for a heat-resistant label according to any    one of items 1 to 5 further comprising an inorganic filler (D).-   Item 7. A composition for a heat-resistant label according to item 1    comprising a silicone resin (A), at least one    high-temperature-adhering inorganic powder selected from the group    consisting of zinc powder, tin powder, and aluminum powder (B-2),    and a solvent (C).-   Item 8. A composition for a heat-resistant label according to item 1    or 7, wherein the weight ratio of the silicone resin (A): the at    least one high-temperature-adhering inorganic powder selected from    the group consisting of zinc powder, tin powder and aluminum powder    (B-2) is about 1:5 to about 10:1.-   Item 9. A composition for a heat-resistant label according to item 1    comprising a silicone resin (A), a polymetallocarbosilane resin    (B-1), at least one high-temperature-adhering inorganic powder    selected from the group consisting of zinc powder, tin powder, and    aluminum powder (B-2), and a solvent (C).-   Item 10. A composition for a heat-resistant label according to any    one of items 1 to 6, and 9, wherein the polymetallocarbosilane resin    (B-1) is at least one member selected from the group consisting of    polytitanocarbosilane resins and polyzirconocarbosilane resins.-   Item 11. A composition for a heat-resistant label according to any    one of items 1 to 6, 9, and 10, wherein the polymetallocarbosilane    resin (B-1) has a weight-average molecular weight of about 500 to    about 10000.-   Item 12. A heat-resistant label having a sticking layer on a    sticking side of a support, the sticking layer comprising a hardened    coating film comprising a silicone resin (A) and at least one member    selected from the group consisting of a polymetallocarbosilane    resin, zinc powder, tin powder, and aluminum powder (B).-   Item 13. A heat-resistant label according to item 12, wherein the    hardened coating film is obtained by applying to the support a    composition of any one of items 1 to 11 and evaporating off the    solvent contained in the composition.-   Item14. A heat-resistant label according to item 12, wherein the    hardened coating film comprises a silicone resin (A) and a    polymetallocarbosilane resin (B-1).-   Item 15. A heat-resistant label according to item 12, wherein the    hardened coating film comprises a silicone resin (A) and at least    one high-temperature-adhering inorganic powder selected from the    group consisting of zinc powder, tin powder, and aluminum powder    (B-2).-   Item 16. A heat-resistant label according to item 12, wherein the    hardened coating film comprises a silicone resin (A), a    polymetallocarbosilane resin (B-1), and at least one    high-temperature-adhering inorganic powder selected from the group    consisting of zinc powder, tin powder, and aluminum powder (B-2).-   Item 17. A heat-resistant label according to any one of items 12 to    16, wherein the sticking layer has a thickness of about 5 μm to    about 100 μm.-   Item 18. A heat-resistant label according to any one of items 12 to    17, wherein the support has a thickness of about 5 μm to about 100    μm.-   Item 19. A heat-resistant label according to any one of items 12 to    18, wherein the support is an aluminum foil, stainless steel foil,    or copper foil.-   Item 20. A heat-resistant label according to any one of items 12 to    19 having a heat-resistant label base layer on a display side of the    support.-   Item 21. A heat-resistant label according to item 20, wherein the    label base layer is a cured coating film comprising a silicone    resin (A) and a polymetallocarbosilane resin (B-1).-   Item 22. A heat-resistant label according to item 20 or 21, wherein    the label base layer is a cured coating film obtained by applying to    the support a composition of any one of items 2 to 6 and heating the    composition.-   Item 23. A heat-resistant label according to any one of items 20 to    22, wherein the label base layer has a thickness of about 0.5 μm to    about 100 μm.-   Item 24. A heat-resistant label according to any one of items 20 to    23 having an identification part on the label base layer.-   Item 25. An article to which a heat-resistant label of any one of    items 12 to 24 is attached through a cured sticking layer.-   Item 26. A method for producing a heat-resistant label, the method    comprising the steps of: applying a composition of any one of items    1 to 11 to a sticking side of a support; and drying the applied    composition to form a hardened coating film.-   Item 27. A production method according to item 26, wherein the    applied composition is dried at about 50° C. to about 240° C.-   Item 28. A production method according to item 26 or 27, comprising,    prior to the step of applying a composition of any one of items 1 to    11 to a sticking side of a support, the steps of: applying a    composition for a heat-resistant label base layer to a display side    of a support; and drying the applied composition to form a cured    coating film.-   Item 29. A production method according to item 28, wherein the    composition for a label base layer is a composition of any one of    items 2 to 6.-   Item 30. A method for producing an article with a heat-resistant    label attached, the method comprising the step of attaching a    heat-resistant label of any one of items 12 to 24 to an article at    about 300° C. to about 670° C.-   Item 31. A heat-resistant label comprising a support and a metal    foil layer comprising at least one member selected from the group    consisting of an aluminum foil, aluminum-alloy foil, tin foil, and    tin-alloy foil, the metal foil layer being laminated on a sticking    side of the support.-   Item 32. A heat-resistant label according to item 31, wherein the    metal foil layer is laminated on the support through an adhering    layer.-   Item 33. A heat-resistant label according to item 31 or 32, wherein    the metal foil layer has a thickness of 5 μm to 100 μm.-   Item 34. A heat-resistant label according to any one of items 31 to    33, wherein the support is a stainless steel foil, copper foil, or    iron foil.-   Item 35. A heat-resistant label according to any one of items 31 to    34, comprising a heat-resistant label base layer on a display side    of the support.-   Item 36. A heat-resistant label according to item 35, wherein the    label base layer has a thickness of about 0.5 μm to about 1.00 μm.-   Item 37. A heat-resistant label according to item 35 or 36, wherein    the label base layer is a cured coating film obtained by    crosslinking the resins of a composition of any one of items 2 to 6.-   Item 38. A heat-resistant label according to any one of items 35 to    37 comprising an identification part on the label base layer.-   Item 39. An article to which a heat-resistant label of any one of    items 31 to 37 is attached.-   Item 40. A method for producing an article with a heat-resistant    label attached, the method comprising the step of attaching a    heat-resistant label of any one of items 31 to 39 to an article at    about 670° C. to about 1100° C.

Compositions for heat-resistant labels of the present invention comprisea silicone resin (A); at least one member selected from the groupconsisting of a polymetallocarbosilane resin, zinc powder, tin powder,and aluminum powder (B); and a solvent (C).

The invention uses a composition in which at least one member selectedfrom the group consisting of a polymetallocarbosilane resin, zincpowder, tin powder, and aluminum powder (B) and a solvent (C) are mixedwith a silicone resin (A), thereby providing heat-resistant labels thatcan be immediately attached to high-temperature products.

In the invention, the silicone resin (A) has a polyorganosiloxanestructure in its molecule. Examples of silicone resins include straightsilicone resins, modified silicone resins, and silicone adhesives. Suchsilicone resins may be used in combination. Among the above, straightsilicone resins are preferable as a silicone resin (A) to be combinedwith a polymetallocarbosilane resin (B-1). Conversely, siliconeadhesives are preferable as a silicone resin (A) to be combined with atleast one high-temperature-adhering inorganic powder selected from thegroup consisting of zinc powder, tin powder, aluminum powder, andmagnesium powder (B-2) (hereinafter, may be referred to as“high-temperature-adhering inorganic powder (B-2)”.

In order to facilitate the process of applying the resin to a supportduring the preparation of the label, the resin is preferably used in theform of a solvent solution.

The weight-average molecular weight of the silicone resin (A) isgenerally about 1000 to about 5000000, and preferably about 3000 toabout 1000000.

A straight silicone resin includes an organopolysiloxane comprising ahydrocarbon group as a main organic group. The organopolysiloxane maycontain a hydroxyl group. Examples of the foregoing hydrocarbon groupsinclude aliphatic hydrocarbon groups and aromatic hydrocarbon groups.Preferred among the above are C₁₋₅ aliphatic hydrocarbon groups andC₆₋₁₂ aromatic hydrocarbon groups. Such hydrocarbon groups may be usedsingly or in combination.

Examples of the C₁₋₅ aliphatic hydrocarbon groups include methyl, ethyl,propyl, butyl, pentyl, vinyl, allyl, propenyl, butenyl, and pentenylgroups. Examples of the C₆₋₁₂aromatic hydrocarbon groups include phenyl,methylphenyl, ethylphenyl, butylphenyl, tertiary butylphenyl, naphthyl,styryl, allylphenyl, and propenylphenyl groups.

The straight silicone resin may be obtained by hydrolyzing one or moresilane compounds such as a chlorosilane or alkoxysilane comprising theforegoing aliphatic hydrocarbon group or aromatic hydrocarbon group, andthen condensing the hydrolysis products, or by hydrolyzing a mixture ofthe foregoing silane compound with tetrachlorosilane ortetraalkoxysilane, and then co-condensing the hydrolysis product.

Examples of the foregoing chlorosilane compounds includemethyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane,methylethyldichlorosilane, vinylmethyldichlorosilane,vinyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane,methylphenyldichlorosilane, vinylphenyldichlorosilane, etc.

Examples of the foregoing alkoxysilane compounds includemethyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,trimethylmethoxysilane, vinylmethylmethoxysilane, vinyltributoxysilane,phenyltriethoxysilane, diphenyldimethoxysilane,methylphenyldipropoxysilane, vinylphenyldimethoxysilane, etc.

The modified silicone resin is an organopolysiloxane containing anorganic group other than a hydrocarbon group. Examples of the modifiedsilicone resin include methoxy-containing silicone resins,ethoxy-containing silicone resins, epoxy-containing silicone resins,alkyd resin-modified silicone resins, acrylic resin-modified siliconeresins, polyester resin-modified silicone resins, epoxy resin-modifiedsilicone resins, etc.

These modified silicone resins can be obtained by, for example, reactingthe hydroxyl group of the foregoing straight silicone resin with anorganic compound having a functional group reactive to the hydroxylgroup, such as carboxyl, acid anhydride, hydroxyl, aldehyde, epoxy, andchloride groups; by copolymerizing a straight silicone resin containingan unsaturated hydrocarbon group, such as a vinyl group, with a compoundhaving an unsaturated double bond; by hydrolyzing a modified silanecompound obtained by the reaction of the foregoing silane compound withanother organic compound so that it undergoes condensation orco-condensation, or the like. The organic compound to be reacted may bea low molecular weight compound or a high molecular weight compound suchas a resin.

Any silicone adhesive can be used without limitation. For example,silicone adhesives comprising a straight chain polyorganosiloxane with amain chain RSiO unit (D unit); a three-dimensional polyorganosiloxanewith R₃SiO_(0.5) unit (M unit) and SiO₂ unit (Q unit); and a hardenerare mentioned. As a hardener, benzoylperoxide, etc., maybe used.Moreover, addition reaction-curing type silicone adhesives using aplatinum catalyst comprise a straight chain polyorganosiloxane with amain chain R₂SiO unit having a vinyl group; a three-dimensionalpolyorganosiloxane with R₃SiO_(0.5) unit and SiO₂ unit;polyorganohydroxysiloxane; a reaction control agent, etc. and a curingcatalyst such as a platinum compound. R is a monovalent organic group.

Since silicone adhesives have a sticking ability even at 0° C., thecomposition of the invention containing such a silicone adhesive as acomponent (A) also exhibits a sticking ability even at about 0° C.Therefore, labels with a hardened coating film made of the compositionas a sticking layer can be attached to an attachment target even attemperatures of about 0° C. to about 300° C., in addition tohigh-temperature conditions. Thus, when a hardened coating filmcomprising a silicone adhesive is employed as a sticking layer, thesticking layer sticks to the target even at room temperature. In view ofthis, laminating a release film to the sticking layer can prevent labelsfrom sticking to objects other than the attachment target during periodsof non-use, and thus this is preferable.

Examples of the silicone resin (A) include dimethylpolysiloxane,methylphenylpolysiloxane, polydimethylsiloxane,polydimethyldiphenylsiloxane, diphenylmethylphenylsilicone resins, etc.

The polymetallocarbosilane resin (B-1) has a crosslinked structureobtained by, for example, reacting polycarbosilane with metal alkoxide.Examples of the above-mentioned metal include titanium, zirconium,molybdenum, chromium, etc., and among these titanium and zirconium arepreferable. Preferred examples of the polymetallocarbosilane resin arepolytitanocarbosilane resins, polyzirconocarbosilane resins, etc. Inorder to improve its coating property, the polymetallocarbosilane resinis preferably mixed with a solvent, such as toluene, xylene, etc. As amixture comprising the polytitanocarbosilane resin, for example, a“Tyranno coat VS-100”, “Tyranno coat VN-100”, etc. manufactured by UbeIndustries, Ltd., can be used. The weight-average molecular weight ofthe polymetallocarbosilane resin is preferably about 500 to about 10000,and more preferably about 700 to about 3000.

In the composition of the invention, there is no limitation to theproportion of the polymetallocarbosilane resin (B-1). The weight ratioof the silicone resin (A):the polymetallocarbosilane resin (B-1) ispreferably about 1:9 to about 9:1, and more preferably about 7:3 toabout 2:8. The composition obtained by mixing these two resins withinsuch a range is favorable for label attachment under high temperatureconditions.

The shape of the at least one high-temperature-adhering inorganic powderselected from the group consisting of zinc powder, tin powder, andaluminum powder powder (B-2) is not limited to a spherical shape,fibrous shapes, laminar shapes, etc. Accordingly, single-crystalinorganic fibers with relatively high aspect ratio such as whiskers areencompassed by the high-temperature-adhering inorganic powder (B-2). Themean particle diameter of the high-temperature-adhering inorganic powder(B-2) is usually 0.05 μm to 100 μm, preferably 1.0 μm to 10 μm, and morepreferably 1 μm to 5μm.

The proportion of the high-temperature-adhering inorganic powder (B-2)is not limited, and is usually 10 parts by weight to 500 parts byweight, preferably 150 parts by weight to 400 parts by weight, and morepreferably 200 parts by weight to 350 parts by weight, per 100 parts byweight of resin component (s). In view of this, when the silicone resin(A) alone is contained as a resin component in the composition of theinvention, the proportion of the high-temperature-adhering inorganicpowder (B-2) is within such a range based on 100 parts by weight of thesilicone resin (A) alone. When the silicon resin (A) and thepolymetallocarbosilane resin (B-1) are contained in the composition, theproportion of the high-temperature-adhering inorganic powder (B-2) iswithin such a range based on 100 parts by weight of the total amount ofthe silicon resin (A) and the polymetallocarbosilane resin (B-1).

In the invention, the solvent (C) has a function of dissolving ordispersing components in the composition to adjust the viscositythereof. Usable as the solvent (C) are, for example, toluene, xylene,cellosolve acetate, ethyl acetate, butyl carbitol, MEK (methyl ethylketone), MIBK (methyl isobutyl ketone), etc. Among these, xylene andtoluene are preferable. The proportion of the solvent (C) is not limitedinsofar as a heat-resistant label can be produced using the compositionof the invention. Thus, the proportion of the solvent (C) can beappropriately adjusted in such a manner that the viscosity of thecomposition of the invention is suitable for application to the supportand drying.

The proportion of the solvent (C) is not limited, and is usually 40parts by weight to 900 parts by weight, preferably 200 parts by weightto 400 parts by weight, and more preferably 230 parts by weight to 350parts by weight, per 100 parts by weight of resin component(s). In viewof this, when the silicone resin (A) alone is contained as a resincomponent in the composition of the invention, the proportion of thesolvent (C) is within such a range, based on 100 parts by weight of thesilicone-resin (A) alone. When the silicon resin (A) and thepolymetallocarbosilane resin (B-1) are contained in the composition, theproportion of the solvent (C) is within such a range, based on 100 partsby weight of the total amount of the silicon resin (A) and thepolymetallocarbosilane resin (B-1).

An inorganic filler (D) can be added, if required, to the composition ofthe invention. The heat-resistance of the heat-resistant label can beenhanced by mixing an inorganic filler (D) since thermal expansion andshrinkage of the heat-resistant label can be thereby reduced. Thus, aninorganic filler (D) is preferably mixed with the composition of theinvention which comprises a polymetallocarbosilane resin and which isused as a label base layer. In order to increase the contrast with anidentification part, white inorganic fillers (D) are especiallypreferable. The label base layer can be colored by using a color pigmentas the inorganic filler (D). Such inorganic fillers (D) can be usedsingly or in combination. The particle diameter of the inorganic fillers(D) is preferably about 0.01 μm to 200 μm, and more preferably about 0.1μm to about 100 μm. The inorganic filler (D) is not limited in shape,and, for example, a spherical shape, fibrous shapes, laminar shapes,etc. are mentioned. Single-crystal inorganic fibers of high aspectratio, such as potassium-titanate whiskers, can be mentioned as anexample of the inorganic filler (D).

The proportion of the inorganic filler (D) is not limited, and isusually 10 parts by weight to 500 parts by weight, preferably 150 partsby weight to 400 parts by weight, and more preferably 200 parts byweight to 350 parts by weight, per 100 parts by weight of resincomponent(s). In view of this, when the silicone resin (A) alone iscontained as a resin component in the composition of the invention, theproportion of the inorganic filler (D) is within such a range, based on100 parts by weight of the silicone resin (A) alone. When the siliconresin (A) and the polymetallocarbosilane resin (B-1) are contained inthe composition of the invention, the proportion of the inorganic filler(D) is within such a range, based on 100 parts by weight of the totalamount of the silicon resin (A) and the polymetallocarbosilane resin(B-1). Alternatively, when the high-temperature-adhering inorganicpowder (B-2) is contained in the composition of the invention, theproportion of the inorganic filler (D) is determined in such a mannerthat the total amount of the high-temperature-adhering inorganic powder(B-2) and the inorganic filler (D) is within such a range. When theinorganic filler (D) is combined with (B-2), the weight ratio of theinorganic filler (D) and the high-temperature-adhering inorganic powder(B-2) is preferably 0.05:1 to 1:1, and more preferably 0.1:1 to 1:1.

An inorganic pigment is used preferably as the inorganic filler (D). Forexample, usable are white substances, such as silica, titanium dioxide,alumina, zirconia, mica, calcium oxide, zinc sulfide-barium sulfate(lithopone), talc, clay, kaolin, calcium carbonate, etc. Moreover,usable are metal compounds, such as carbonates, nitrates, sulfates,etc., which are oxidized to form such white substances in a heattreatment during the production of the heat-resistant label. Also,usable as the inorganic powder (D) are reddish-brown substancescontaining metal ion such as iron, copper, gold, chromium, selenium,zinc, manganese, aluminum, tin, etc. (e.g., zinc oxide-ironoxide-chromium oxide, manganese oxide-alumina oxide, chromium oxide-tinoxide-iron oxide, etc.); blue substances containing metal ion such asmanganese, chromium, aluminum, cobalt, copper, iron, zirconia, vanadium,etc. (e.g., cobalt oxide-aluminum oxide, cobalt oxide-aluminumoxide-chromium oxide, cobalt oxide, zirconia-vanadium oxide, chromiumoxide-divanadium pentoxide, etc.); black substances containing metal ionsuch as iron, copper, manganese, chromium, cobalt, aluminum, etc. (e.g.,copper oxide-chromium oxide-manganese oxide, chromium oxide-manganeseoxide-iron oxide, chromium oxide-cobalt oxide-iron oxide-manganeseoxide, chromate, permanganate, etc.); yellow substances containing metalion such as vanadium, zinc, tin, zirconium, chromium, titanium,antimony, nickel, praseodymium, etc. (e.g., titanium oxide-antimonyoxide-nickel oxide, titanium oxide-antimony oxide-chromium oxide, zincoxide-iron oxide, zirconium-silicon-praseodymium, vanadium-tin,chromium-titanium-antimony, etc.); green substances containing metal ionsuch as chromium, aluminum, cobalt, calcium, nickel, zinc, etc. (e.g.,titanium oxide-zinc oxide-cobalt oxide-nickel oxide, cobaltoxide-aluminum oxide-chromium oxide-titanium oxide, chromium oxide,cobalt-chromium, alumina-chromium, etc.); pink substances containingmetal ion such as iron, silicon, zirconium, aluminum, manganese, etc.(e.g., aluminum-manganese, iron-silicon-zirconium, etc.). Among these,preferable are talc, clay, kaolin, titanium dioxide, alumina, zincoxide-iron oxide-chromium oxide, titanium oxide-antimony oxide-nickeloxide, titanium oxide-antimony oxide-chromium oxide, zinc oxide, ironoxide, zinc oxide-iron oxide-chromium oxide, titanium oxide-zincoxide-cobalt oxide-nickel oxide, cobalt oxide-aluminum oxide-chromiumoxide, cobalt oxide-aluminum oxide, cobalt oxide-aluminum oxide-chromiumoxide, copper oxide-chromium oxide-molybdenum oxide, copperoxide-chromium oxide-manganese oxide, copper oxide-manganese oxide-ironoxide. A label produced using kaolin is especially preferable since anidentification part to be printed on the label base layer is not easilypeeled off even when the label contacts fibers of the head of a labelattaching machine at the time of attachment.

A dispersant (E) is preferably mixed into the composition forheat-resistant labels of the invention. This is because the dispersionrate is improved by mixing a dispersant, thereby facilitatingpreparation of the composition. Usable as the dispersant (E) arealiphatic polyvalent carboxylic acids, amine salts of polyester acids,long-chain amine salts of polycarboxylic acids, amine salts of polyetherester acids, amine salts of polyether phosphates, polyether phosphates,amide amine salts of polyester acids, etc. The dispersant (E) isgenerally used in a proportion of about 0.01 parts by weight to about 5parts by weight, preferably about 0.1 parts by weight to about 2 partsby weight, per 100 parts by weight of the high-temperature-adheringinorganic powder (B-2) and inorganic filler (D). In view of this, wheneither one of the high-temperature-adhering inorganic powder (B-2) orinorganic filler (D) is contained in the composition of the invention,the proportion of the dispersant (E) is within such a range based on 100parts by weight of total amount of the above. When both thehigh-temperature-adhering inorganic powder (B-2) and inorganic filler(D) are contained in the composition of the invention, the proportion ofthe dispersant (E) is within such a range, based on the total amount ofthe high-temperature-adhering inorganic powder (B-2) and inorganicfiller (D).

Additives, such as crosslinking agents, plasticizers, etc., can also beadded as needed to the composition for heat-resistant labels of theinvention within ranges that do not adversely affect the effects of theinvention, in addition to the silicone resin (A), at least one memberselected from the group consisting of the polymetallocarbosilane resin,zinc powder, tin powder, and aluminum powder (B), the solvent (C), theinorganic filler (D), and the dispersant (E).

Examples of crosslinking agents include boric acid compounds,organometallic compounds, etc. Boric acid compounds are compoundscontaining a boric acid residue in its molecule, and include boricacids, borates, borate esters, etc. Boric acids include orthoboric acid,metaboric acid, anhydrous boric acid, etc. Borates include sodiumborate, potassium borate, magnesium borate, calcium borate, zinc borate,aluminum borate, etc. Borate esters include methyl borate, ethyl borate,butyl borate, octyl borate, dodecyl borate, etc. Among such compounds,orthoboric acid is particularly preferable.

Examples of organometallic compounds include organonickel compounds,organoiron compounds, organocobalt compounds, organomanganese compounds,organotin compounds, organolead compounds, organozinc compounds,organoalumminum compounds, organotitanium compounds, etc., and amongthese, chelate compounds are preferable. Crosslinking agents arepreferably mixed in an amount such that the amount of metal contained inthe crosslinking agent is about 0.05 parts by weight to about 10 partsby weight, preferably about 0.1 parts by weight to about 5 parts byweight, per 100 parts by weight of the total amount of the resin (A) andthe resin (B).

Examples of plasticizers include aliphatic esters, aromatic esters,phosphate esters, etc. Specific examples of aliphatic esters includemethyl laurate, butyl oleate, diethylene glycol dilaurate,di(2-ethylbuthoxyethyl)adipate, etc. Specific examples of aromaticesters include dimethyl phthalate, dioctyl phthalate, di(2-ethylhexyl)phthalate, dilauryl phthalate, oleyl benzoate, phenyloleate, etc. Specific examples of phosphate esters include tricresylphosphate, trioctyl phosphate, etc. The addition of such plasticizerscan provide a further improvement in the flexibility of the label baselayer.

The composition of the invention can be prepared by mixing anddispersing the above-mentioned components. The components can bedispersed by a dispersion mill, such as a bead mill, a ball mill, a sandmill, a roll mill, etc. The grain size of the dispersion in thedistributor is preferably about 0.01 to about 200 μm, more preferablyabout 0.1 to about 20 μm.

The composition of the invention can be used as a starting material forthe sticking layer of the heat resistant label of the invention which issuitable for use at temperatures of 300° C. or higher. Morespecifically, the sticking layer is formed by applying the compositionof the invention to one side (sticking side) of a support, and dryingthe applied composition until the solvent in the composition is removedso as to form a hardened coating film. The composition of the inventioncomprising the silicone resin (A) and the polymetallocarbosilane resin(B-1) can also be used as a starting material for forming the label baselayer of the heat-resistant label of the invention. More specifically,the label base layer is formed by applying the composition of theinvention to one side of the support, and drying the applied compositionat a temperature at which the resins in the composition are crosslinkedin such a manner as to form a cured coating film.

In this specification, a hardened coating film represents a film whichis obtained by drying the composition of the invention until the solventin the composition is substantially removed, and which can function as asticking layer at temperatures of 300° C. or higher. In other words, thehardened coating film has a sticking ability at temperatures of 300° C.or higher (i.e., high-temperature sticking coating film). Crosslinkingof the resins may proceed in such a manner that functionality as thesticking layer is demonstrated. Any remaining solvent might raise thepossibility of ignition under high temperature conditions. Therefore,the amount of solvent remaining in the hardened coating film is usuallyabout 0.1% by weight or less, preferably 0.0001% by weight or less.Crosslinking of the resins in the composition may occur in the dryingprocess for removing the solvent. In the case of excessive crosslinkingthereof, the film is cured, and thus the sticking ability is lost underhigh temperature conditions. Therefore, it is important to conduct thedrying process under the drying conditions for forming the hardenedcoating film where the solvent is remove and the sticking function ismaintained even under high temperature conditions, even if crosslinkingproceeds.

The cured coating film of the composition of the invention comprisingthe polymetallocarbosilane resin (B-1) is useful for the label baselayer of the heat-resistant label. For example, it can be used as alabel base layer of the following heat-resistant label of the invention.A label is known whose support, such as a stainless steel foil or thelike, is attached to a target by welding (spot welding, etc.); howeverthe above-mentioned cured coating film can also be used as a label baselayer that is attached by welding.

In this specification, a cured coating film represents a film which isobtained by drying the composition of the invention until the solvent inthe composition is substantially removed and the film is cured to anextent that the film does not adhere to a label attaching machine and,if it is used-as a label base layer with an identification part, theidentification part is kept, at temperatures of 300° C. or higher in theattachment process. In other words, the cured coating film does notstick at temperatures of 300° C. or higher (i.e., a high-temperaturenon-sticking coating film). In order to avoid the film from sticking tothe label attaching machine, the film needs to be cured. Thus, theheating conditions for forming the cured coating film needs to be moresevere than those for the hardened coating film.

High-temperature-adhering metal powder (tin, zinc, aluminum) maydemonstrate a sticking ability under high-temperatures, and thus it ispreferable that such metal powders are not mixed with a label baselayer.

The heat-resistant label of the invention is suitable for attachment toa target having temperatures of about 300° C. or higher (preferably,350° C. or higher, and more preferably 400° C. or higher) at the timingof attachment. Further, the heat-resistant label of the invention has afeature of providing, on a sticking side of the support, a stickinglayer comprised of the hardened coating film comprising the siliconeresin (A), and at least one member selected from the group consisting ofthe polymetallocarbosilane resin, zinc powder, tin powder, and aluminumpowder (B). The heat-resistant labels of the invention are roughlyclassified into heat-resistant labels which are suitable for hightemperature targets (about 300° C. to about 670° C.), and those suitablefor very high temperature targets (about 670° C. to about 1100° C.,hereinafter, these may be referred to as “super heat-resistant labels”).In this specification, the former is sometimes referred to as“heat-resistant label 1” and the latter as “heat-resistant label 2”.

The heat-resistant label 1-1 of the invention has a feature of having asticking layer, which is made of a hardened coating film comprising thesilicone resin (A) and polymetallocarbosilane resin (B-1), on one side(sticking side) of the support. Such a label has, as a sticking layer, ahardened coating film obtained by applying the above-mentionedcomposition of the invention comprising, for example, the silicone resin(A) and polymetallocarbosilane resin (B-1) to a sticking side of thesupport, and drying the solvent of the applied composition. The stickinglayer of the heat-resistant label 1-1 may comprise at least one memberselected from the group consisting of zinc powder, tin powder, andaluminum powder, and further comprise an inorganic filler.

The heat-resistant label 1-2 of the invention has a feature such that asticking layer, which is made of a hardened coating film comprising thesilicone resin (A) and at least one high-temperature-adhering inorganicpowder selected from the group consisting of zinc powder, tin powder,and aluminum powder (B-2) is placed on a sticking side of the support.Such a label is provided as a sticking layer with a hardened coatingfilm obtained by applying the above-mentioned composition of theinvention comprising, for example, the silicone resin (A) andhigh-temperature-adhering inorganic powder (B-2) to a sticking side ofthe support, and drying the solvent of the applied composition.

The heat-resistant labels 1-1 and 1-2 can be provided with aheat-resistant label base layer on the other side (display side) of thesupport, on which no sticking layer is provided. When a label base layeris not provided, an identification part, such as a bar code or the like,can be provided directly onto the support.

The support of the heat-resistant label 1 of the invention is made of afilm-like and-heat-resistant material, and a metal foil is preferable.Minute pores maybe formed in the support. Forming pores makes it easy toevacuate gas produced when resins contained in the sticking layer andlabel base layer laminated on the support decompose at hightemperatures, thereby suppressing expansion of the label base layer. Asupport made of the same material as the label attaching target givesthe label a comparatively high resistance against thermal expansion andshrinkage, and thus the label is prevented from peeling off under hightemperature conditions. Examples of metal foils include aluminum foil,stainless steel foil, copper foil, iron foil, etc. Among these, thealuminum foil is preferably used as the support. The thickness of thesupport is usually about 5 to about 100 μm, preferably about 10 to about70 μm, and more preferably about 10 μm to about 60 μm. When thethickness of the support is within such a range, breakage of the labelis suppressed due to further reduced thermal expansion or thermalcontraction, and furthermore, due to the flexibility, the label can beattached in accordance with the shape of the target.

Examples of aluminum foils include JIS (Japanese Industrial Standard)alloys 1N30, 1085, 1N90, 1N99, 3003, 3004, 5052, 8079, and 8021, etc.,with 1N30 being preferable.

Examples of stainless steel foils include martensite-based (SUS410,SUS440), ferrite-based (SUS430, SUS444), austenite-based (SUS304,SUS316), two-sided based (SUS329J1, SUS329J4L) foils, SUS630, andSUS631, etc.

JIS SPHC, SPCC, SECC, SGCC, SZACC, SA1C, etc. can be used as othermetals, and among these, SPHC and SPCC Standard are preferable.

Easily available commercial metal foils can be used as theabove-described supports.

In the heat-resistant label 1 of the invention, the sticking layer isthe above-described hardened coating film. More specifically, such afilm is obtained by drying the composition of the invention until thesolvent in the composition is at least substantially removed, and servesas a sticking layer without the possibility of ignition under hightemperature conditions of 300° C. or higher.

The temperature and period for drying the composition of the inventionto form the sticking layer are not limited insofar as the composition ofthe invention is dried and the resultant end product serves as asticking layer under high temperature conditions. Thus, the temperatureand period are appropriately changed according to the thickness and thesolvent content of the coating film obtained by applying the compositionof the invention, and material and the thickness of the support. Forexample, drying may be carried out with a convection oven at about 50 toabout 240° C., preferably at about 80 to about 200° C., for about 1minute to about 60 minutes, and preferably about 1 minute to about 20minutes. The drying period can be suitably adjusted according to theflow of hot air.

The thickness of the sticking layer after drying is usually about 5 μmto about 100 μm, preferably about 10 μm to about 60 μm. When the dryfilm thickness of the sticking layer is within such a range, thesticking layer is strongly stuck to the target, thereby inhibitingcohesion failure of the sticking layer.

The heat-resistant label 1 of the invention has a sticking layer on asticking side of the support-, and a heat-resistant label base layer canbe formed on the other side (display side) of the support. Anyconventionally used or reported films obtained by drying compositionsfor the formation of the label base, such as a composition comprising,for example, a silicone resin, inorganic powder, and organic solvent,can be used as the label base layer insofar as it can withstandtemperatures of 300° C. or higher. A cured coating film obtained byheating the composition of the invention can also be used as the labelbase layer. The label base layer can be formed by applying thecomposition of the invention to the display side of the support andheating the applied composition until the solvent of the composition issubstantially removed and the resins in the composition are crosslinked,so as to form a cured coating film.

When the composition of the invention is used for forming the label baselayer, the temperature and period for heating the composition of theinvention are not limited insofar as the composition of the invention isdried and the resultant end product serves as the label base layer underhigh temperature conditions. Thus, the heating temperature and periodare appropriately varied according to the thickness and solvent contentof the coating film obtained by applying the composition of theinvention to the support, and the material and thickness of the support.For example, heating may be carried out with a convection oven at about245 to about 500° C., preferably at about 250 to about 400° C. for about1 minute to about 40 minutes, preferably about 2 minutes to about 20minutes. The drying period can be suitably adjusted according to theflow of hot air. The thickness of the label base layer after heating isgenerally about 0.5 μm to about 100 μm, and preferably about 1 μm toabout 60 μm.

To produce the heat-resistant label 1 with the label base layer obtainedby curing the composition of the invention, the label base layer isfirst formed on the display side of the support, and subsequently thesticking layer is formed on the sticking side of the support. When thelabel base layer is formed after the sticking layer, both the layers aremade into a cured coating film due to the severer heating conditions forforming the label base layer than those for forming the sticking layer.In such a case, the heat-resistant label cannot be attached under hightemperature conditions. When the label base layer is formed using theconventional composition for forming the label base, the order offorming the layers can be suitably determined considering the dryingconditions applied to this composition and the sticking layer.

The method for manufacturing the heat-resistant label 1 of the inventioncomprises: applying the composition of the invention to one side of thesupport; and drying the applied composition to form a hardened coatingfilm.

The composition of the invention is applied to a sticking side ordisplay side of the support by, for example, a printing method such asscreen-printing, etc., a roll coater method, gravure roll coater method,doctor blade method, bar coater method, etc. Screen-printing, gravureroll coating, and bar coating methods are preferable as applicationmethods. The composition of the invention is applied to the support, anddried to form a hardened coating film (sticking layer). The dryingconditions are the same as those for the sticking layer.

The method for producing the heat-resistant label 1 with the label baselayer of a cured coating film obtained by curing the composition of theinvention comprises, prior to applying the composition of the inventionto the sticking side of the support in the above-mentioned productionmethod: applying the composition for the heat-resistant label base layerto the display side of the support; and heating the applied compositionto form a cured coating film.

When the composition of the invention is used as a composition for aheat-resistant label base layer, the step of applying the compositionfor the heat-resistant label base layer may be carried out in the samemanner as the above-described step of applying the composition of theinvention. The step of curing the composition of the invention byheating is curried out under the same conditions as the above-describedconditions for forming the label base layer.

A conventional composition for a label base layer may be used as thecomposition for the heat-resistant label base formation. In this casealso, the conventional composition can be applied in the same manner asthe above-described step of applying the composition of the invention tothe display side of the support. In the curing step, the heatingconditions can be suitably varied according to the composition used.

The heat-resistant label 2 of the invention has a support and a metalfoil layer, and the metal foil layer is made of at least one metal foilselected from the group consisting of an aluminum foil, an aluminumalloy foil, a tin foil, and a tin alloy foil (hereinafter, may bereferred to as “adhering metal foil”) on one side (adhering side) of thesupport, and is suitable for the use at about 670° C. to about 1100° C.,and preferably about 700° C. to about 1000° C. With tin foil or tinalloy foil, the heat-resistant label 2 can be used at about 300° C. toabout 670° C. in addition to the above range of about 670° C. to about1100° C. An adhering layer for adhering the adhering metal foil layer tothe support may be provided between the support and the adhering metalfoil layer. The heat-resistant label 2 is stuck to the attachment targetwhen the adhering metal foil is melted under high temperatureconditions. A label having an aluminum layer that is formed by thermallyspraying aluminum onto the support surface does not stick to the target,since the aluminum layer does not melt at the temperature of theattachment target. This is because the melting temperature of of thelayer obtained by thermal spraying is elevated by oxidization of thesurface, whose area is increased by thermal spraying.

A film-like material which does not melt within the temperature rangedesirable for the label is usable for the support of the heat-resistantlabel 2,and a metal foil is preferable. A support made of the samematerial as the label attaching target gives the label further improvedresistance against thermal expansion and shrinkage. Examples of metalfoils include stainless steel foil, copper foil, iron foil, etc. Amongthese, stainless steel foil is preferable. The thickness of the supportis usually about 5 μm to about 100 μm, preferably about 10 μm to about50 μm, and more preferably about 10 μm to about 40 μm. When thethickness of the support is within such a range, breakage of the labelis sufficiently suppressed due to further reduced thermal expansion orthermal shrinkage, and furthermore, due to the flexibility, the labelcan be attached in accordance with the shape of the target. Examples ofstainless steel foils are the same as in the support of theheat-resistant label 1. The same applies to the other metal foils.

The heat-resistant label 2 can be attached when the adhering metal foillayer is melted at high temperatures. Accordingly, the adhering metalfoil layer is formed on to only one side of the support. The thicknessof the adhering metal foil layer is usually about 1 μm to about 300 μm,preferably about 10 μm to about 100 μm. An aluminum foil layer ispreferable as the adhering metal foil layer. Examples of aluminum foilsinclude, JIS alloys 1N30, 1085, 1N90, 1N99, 3003, 3004, 5052, 8079, and8021, etc., and among these, 1N30 is preferable. In aluminum-alloy foil,the proportion of aluminum in the alloy is usually 50% by weight to 99%by weight, and preferably 70% by weight to 99% by weight. The sameapplies to tin-alloy foil so that, in tin-alloy foil, the proportion oftin in the alloy is usually 50% by weight to 99% by weight, andpreferably 70% by weight to 99% by weight. Any aluminum alloy can beused insofar as it is alloy of aluminum and another metal (s), and meltsat temperatures favorable for the use of the heat-resistant label 2. Aswith in the case of aluminum alloys, any tin alloy can be used insofaras it is alloy of tin and another metal(s), and melts at temperaturesfavorable for the use of the heat-resistant label 2. The meltingtemperature can be adjusted by alloying. For example, usable arealuminum alloy foils of aluminum with at least one metal selected fromthe group consisting of zinc, tin, indium, copper, nickel, and silver.Among these, alloys of aluminum with zinc and alloys of aluminum withtin are preferable.

The adhering metal foil layer is laminated on the support by, forexample, a method of adhering the adhering metal foil layer to thesupport with an adhering layer composed of a resin, etc. There is nolimitation to the area of the adhering metal foil layer to be adhered tothe support, insofar as the support is attached to an attachment target.The area of the adhering metal foil layer occupies usually 10% to 100%,and preferably 20% to 100%, of the area of the support. The adheringmetal foil layer is not limited in shape insofar as the support isadhered to an attachment target. The adhering metal foil layer can belaminated onto the support in such a manner as to cover the entiresurface thereof. Alternatively, an adhering metal foil layer with around shape, rectangular shape, etc. can be laminated onto the center ofthe support so as to occupy about 50% of the area of the support. Whenthe support is square, adhering metal foil layers with a round shape,rectangular shape, etc. with an area occupying about 10% of the area ofthe support can be successively placed at the four corners of thesupport.

Through such an adhering layer, the adhering metal foil is adhered tothe support. Any adhering layer may be used without limitation insofaras the adhering metal foil is adhered to the support, until the adheringmetal foil melts and adheres to the support and target. In general,examples of an adhesive forming the adhering layer include:polyolefin-based resins such as polyethylene (e.g., low-density andhigh-density polyethylenes), polypropylene, polybutene, polyisobutylene,isobutylene maleic anhydride copolymers, polyvinyl acetate,polypropylene chloride, polyvinylidene chloride, polyvinyl ether, etc.;acrylate-based resins such as polymethylmethacrylate, polyacrylic acid,polymethacrylate, polyacrylamide, etc.; polyester-based resins such aspolyethylene terephthalate, polybutylene terephthalate, polyethylenenaphthalate, polycyclohexane dimethyleneterephthalate, etc.;petroleum-based resins such as polycyclopentadiene, etc.; silicone-basedresins such as straight silicone resins, silicone adhesives, modifiedsilicone resins, etc.; phenol-based resins such as 100% phenol resin,novolak-type phenol resins, resol-type phenol resins, etc.; modifiedalkyd resins such as rosin-modified alkyd resins, phenol-modified alkydresins, styrene alkyd resins, silicone-modified alkyd resins, etc. Suchresins can be used singly or in combination. If necessary, the resinscan be dissolved or dispersed in a solvent. In addition to these resins,metal foils with a low melting point can be used. Resins that evaporateor decompose with heat near the temperature at which the adhering metalfoil adheres to the support are preferable as the adhesive constitutingthe adhering layer. Additives, etc. may be suitably added to the resinadhesives in addition to these adhesives.

It is preferable that the adhering layer has sufficient adheringproperty so that the adhering metal foil does not peel off the support.In the case of a resin adhesive, the thickness of the layer after thesolvent is removed is usually about 0.1 μm to about 50 μm, preferablyabout 2 μm to about 10 μm. A thin adhering layer is suitable forevaporating and decomposing the resin-adhesive.

The area of the resin adhesive layer is suitably determined so that theadhering ability is retained to avoid the adhering metal foil frompeeling off the support as described above. The area is preferably 1% to100%, and more preferably 1% to 80%, per the area of the adhering metalfoil. Theadhering metal foil layer directly contacts the support at anadhesive-free portion, if any is present, between the support and theadhering metal foil layer. In this case, the adhering metal foil islikely to melt to adhere to the support under very high temperatures,thereby establishing strong adhesion between the label and theattachment target. For example, a label with an adhering layer which isformed in, for example, a spiral pattern can be firmly adhered to anattachment target.

The adhering metal foil may be adhered to the support using the resinadhesive as follows: the above-mentioned adhesive (to which a solvent isadded, as needed) is applied to the support, followed by drying, andthen the adhering metal foil may be adhered to the support; or theadhesive is applied to the adhering metal foil, followed by drying, andthen the support may be adhered thereto. These methods are preferable inthat the solvent in the adhesives is easily removed by drying.Alternatively, the following processes may be employed: the adhesive isapplied to the support, and then the adhering metal foil is adhered tothe support with the adhesive, followed by drying; or the adhesive isapplied to the adhering metal foil, and then the support may be adheredto the adhering metal foil with the adhesive, followed by drying. Also,usable is a process comprising: sandwiching a resin film between thesupport and the adhering metal foil, and then compressing the same whileheating at a temperature at which the resin is adhered.

Methods for applying the adhesive to the support and adhering metal foilare not limited, and in general printing methods such asscreen-printing, etc.; roll coater methods, gravure roll coater methods,doctor blade methods, bar coater methods, etc. are usable. The adhesiveis dried until the solvent is substantially removed, and the dryingtemperature, drying period, etc. can suitably vary according to theadhesive used.

A metal foil with a low melting point-may be used as the adhesive bysandwiching the metal foil between the support and the adhering metalfoil to form a laminate, and heating the laminate at a temperature atwhich the metal sandwiched melts.

The heat-resistant label 2 of the invention has an adhering metal foillayer on an adhering side of the support, and can be provided with aheat-resistant label base layer on the other side (display side). Anyfilms obtained by drying a conventionally used or reported compositionfor forming the label base, such as a composition comprising a siliconeresin, inorganic powder, organic solvent, etc., can be used as the labelbase layer insofar as the label base layer can withstand a temperaturefavorable for the use of the heat-resistant label 2 (about 670° C. toabout 1100° C.). A cured coating film obtained by drying the compositionof the invention can be used at 1100° C., and thus is preferable as alabel base layer. In this case, the label base layer can be formed byapplying the composition of the invention to the display side of thesupport, and heating the applied composition to form a cured coatingfilm at a temperature at which the solvent in the composition issubstantially removed and the resin in the composition is cross-linked.The label base layer is applied to the support in the same manner as inthe heat-resistant label 1.

After applying the composition of the invention to the support, theapplied composition is cured by heating. The heating temperature andperiod are appropriately varied according to the thickness and solventcontent of the coating film obtained by applying the composition of theinvention to the support, and the material and thickness of the support.For example, heating may be carried out with a convection oven at about245 to about 500° C., preferably at about 250 to about 400° C. for about1 minute to about 40 minutes, preferably about 2 minutes to about 20minutes. The drying period can be suitably adjusted according to theflow of hot air. The thickness of the label base layer after drying isgenerally about 0.5 μm to about 100 μm, preferably about 1 μm to about60 μm.

The label base layer may be formed on a support before the adhesivelayer or adhering metal foil layer is laminated thereon, or may beformed on a support after the adhesive layer or adhering metal foillayer has been laminated thereon.

The heat-resistant labels 1 and 2 have the following points in common.The use of a colored label base layer (e.g., a label base layercomprising inorganic colored powder) permits product management by colorclassification of the products, if such product management is desired,which eliminates the necessity of having an identification part.However, for more precise product management, it is preferable toprovide an identification part on the label base layer. Providing anidentification part allows the heat-resistant label to be used as a datacarrier. Thus, various information can be given to a product byattaching the label provided with an identification part to the product.When the heat-resistant label 1 or 2 is provided with no label baselayer, the identification part is provided on the display side of thesupport.

The identification part is usually formed by printing patterns orimages, such as characters or symbols (bar codes, etc.), onto the labelbase layer using known heat-resistant inks. Labels provided with suchidentification parts can be used as data carrier labels, typified bybar-code labels. Examples of identification parts include anyidentification codes such as 1-dimensional bar-codes -of the UPC,JAN/EAN (JIS-X-0501, ISO/IEC15420), CODE39 (JIS-X-0503, ISO/IEC15388),CODE128 (JIS-X-0504, ISO/IEC15417), ITF (Interleaved 2 of 5)(JIS-X-0502, ISO/IEC15390), NW-7 (Codabar) (JIS-X-0510), and RSS 14(UCC/EAN) codes; 2-dimensional codes of the QR (JIS-X-0510,ISO/IEC18004), Micro QR codes, PDF417 (ISO/IEC15438), DataMatrix(ISO/IEC16022), MaxiCode (ISO/IEC16023), AztecCode (ISS1997), andUCC/EAN composite (USS/EAN, ITS1999); and characters. Among these,1-dimensional and 2-dimesional bar codes are preferable.

Inks capable of withstanding a high-temperature process, i.e., 300° C.or higher, is used as the above-mentioned heat-resistant ink.Heat-resistant inks containing carbon, a metal oxide, etc. as a colorpigment are particularly preferable. Examples of metal oxides for use inthe heat-resistant inks include oxides of metals such as iron, cobalt,nickel, chromium, copper, manganese, titanium, aluminum, etc. These canbe used singly or mixtures thereof. These metal oxides are supplied inthe form of a powder, and the particle size is usually about 0.01 μm toabout 50 μm, preferably about 0.1 μm to about 10 μm.

Heat-resistant inks containing color pigments can be produced by mixinga binder in an amount of about 1 to about 1000 parts by weight,preferably about 10 to about 200 parts by weight, per 100 parts byweight of the color pigment; adding a solvent as needed; and dispersingor kneading the mixture with a dispersion machine, such as a disper,ball mill, roll mill, sand mill, etc., giving a liquid-like orpaste-like mixture. Examples of the binder for use in the process areresins, waxes, fats, oils, low-melting glasses (e.g., glass frits suchas borosilicate glass, soda glass, etc.), etc. Among these, aheat-resistant ink containing a color pigment, glass frit, and organicbinder is preferable.

Examples of such resins include silicone resins, hydrocarbon resins,vinyl resins, acetal resins, imido resins, amide resins, acrylateresins, polyester resins, polyurethane resins, alkyd resins, proteinresins, cellulose resins, etc. For example, organo polysiloxanes,polymetallocarbosilanes, polystyrene, polyethylene, polypropylene,polyvinyl acetate, polyvinyl butyral, polyvinyl formal, polyimides,polyamides, poly(meth)acrylates, gelatin, cellulose derivatives,polyvinyl alcohol, polyvinylpyrrolidone, etc.-are mentioned. These canbe used singly or as mixtures or copolymers thereof.

Examples of waxes include paraffin waxes, natural waxes, higher alcoholwaxes, higher amide waxes, higher fatty acids, ester waxes, etc. Thefollowing examples may be mentioned: paraffin wax, polyethylene wax,yellow wax, carnauba wax, stearyl alcohol, palmityl alcohol, oleylalcohol, stearamide, oleamide, palmitamide, ethylenebisstearamide,stearic acid, oleic acid, palmitic acid, myristic acid, ethyl stearate,butyl palmitate, palmityl stearate, stearyl stearate, etc.

Examples of fats and oils are castor oil, soybean oil, linseed oil,olive oil, beef tallow, lard, mineral oils, etc. Examples of low-meltingglasses include glasses with melting points of 700° C. or lower, glassessoluble in solvents, and more specifically, a glass frit with themelting point of 700° C. or lower and with the particle size of about0.1 μm to about 100 μm, preferably about 0.2 μm to about 50 μm, waterglasses, etc.

The following examples may be mentioned as solvents for use in theprocess of dispersion or kneading: aliphatic hydrocarbons such ashexane, octane, decane, cyclohexane, etc.; aromatic hydrocarbons such asbenzene, toluene, xylene, cumene, naphthalene, etc.; ketones such asacetone, methyl ethyl ketone, cyclohexanone, etc.; alcohols such asmethanol, ethanol, 2-ethylhexanol, etc.; ethers such as ethylene glycolmonomethyl ether, diethylene glycol dibutyl ether, etc.; esters such asmethyl acetate, ethyl formate, ethyl acetoacetate, etc.; petroleumdistillation fractions such as gasoline, kerosene, gas oil, etc.; water;etc. It is preferable to use such solvents for dilution in an amount ofabout 500 parts by weight or less, preferably about 200 parts by weightor less, per 100 parts by weight of the total amount of the colorpigment and binder.

Any patterns, including characters and symbols such as a bar code, maybe formed on the heat-resistant label of the invention using theheat-resistant ink composed of such components by known printingmethods, laser marking, etc. Examples of printing methods includegravure offset printing, plate offset printing, letterpress printing,intaglio printing, silk screen printing, ink-jet printing, ribbonprinting, etc. These printing methods and laser markings may be appliednot only when providing the identification part on the label base layer,but also when providing the identification marker directly onto thesupport.

There is no limitation to the shape of the heat-resistant label of theinvention, and a shape suitable for a label attaching machine forattaching the label under high temperature conditions is preferable. Theheat-resistant label of the invention can be produced by providing othercomponents (the label base layer, sticking layer, adhering layer,adhering metal foil layer, identification part, etc.) to the supportwhich is formed into a shape suitable for attachment to a product, or byproducing a large-scale sheet-like support provided with othercomponents, and then forming the same into a shape suitable forattachment to a product. The forming methods are not limited, andinclude slit processing, punch processing, etc.

There is no limitation to the label attaching machine for attachment ofthe heat-resistant label of the invention, and any machine can be usedinsofar as it can withstand high temperatures. In general, textilesshowing little distortion when exposed to high temperatures (preferably,textiles woven in three dimensions) are used for the label-contactingarea of the head of the label attaching machine. Examples of fibers forsuch textiles include Tyranno fiber, carbon fiber, glass fiber, aluminasilica fiber, etc., and these can be used singly or in combination.Among these, Tyranno fiber is preferable.

When the label is attached to an uneven surface, the following propertyfor the uneven surface is important for the textile for use in the headof the label attaching machine. More specifically, a textile with anexcellent following property for the uneven surface increases the labelcontacting area of the label attachment target, thereby enhancing thelabel adhesion. Thick textiles made of Tyranno fiber have highelasticity and an excellent following property. Thus, thick textilesmade of Tyranno fiber are favorable in view of label adhesiveness.

The inventors conducted cycle tests to evaluate the resistance againstheat and pressure of textiles made of Tyranno fiber under the conditionsdescribed later, and found that textiles made of Tyranno fiber showexcellent resistance against heat and pressure even when they areattached to the product having high temperatures.

Cycle Test for Resistance Against Heat and Pressure

3-D woven Tyranno fiber shaped into a rectangular parallelepiped(vertical×horizontal×height: 80 mm×180 mm×8 mm) was placed in anelectric furnace at 600° C., and then the heated fiber was subjected topressurization (10 seconds, 100 g/cm²), and non-pressurization (6seconds), together defined as one cycle, and 9000 cycles were repeated.The Tyranno fiber was not deteriorated in appearance, and showed afavorable adhesion property.

Next, the product of the invention is now described. The product of theinvention has the heat-resistant label 1 or 2 of the invention attached,and may be either an intermediate product or a finished product. Theheat-resistant labels 1 and 2 of the invention can be adhered toheat-resistant products having a temperature of from about 300° C. toabout 1100° C. over a short period. The attachment period is usuallyabout 1 second to about 2 minutes, preferably about 1 second to-about 1minute, and more preferably about 1 second to 30 seconds. Any productcan be used insofar as the heat-resistant label of the invention can beattached thereto, and the temperature of the product is within the rangeof from about 300° C. to about 1100° C. during the product manufacturingprocess. A heat-resistant label 1 is suitably attached to a producthaving a temperature in the range from about 300° C. to about 670° C. Aheat-resistant label 2 is suitably attached to a product having atemperature in the range of from about 670° C. to about 1100° C., andmore preferably about 700° C. to about 1000° C. The product of theinvention is usually a metal product, ceramic, glassware, etc. Examplesof metal products include primary molded products, such as a metalbillets of steel, aluminum, stainless steel, copper, etc., slabs, coils,H-shaped steels, cylindrical tubes, rods, plates, etc., and secondarymolded products obtained by molding primary molded products by extrusionmolding, casting molding, etc.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is now described below in detail with reference tothe following Examples but is not limited thereto; Materials used inExperiments and Comparative Experiments are as follows.

<Support>

-   Aluminum foil: “1N-30-H-40RT”,-   40 μm thick,-   produced by Nippon Foil Mfg. Co., Ltd.-   Stainless-steel foil: “SUS304 H-TA/MW”,-   20 μm thick,-   produced by Nippon Steel CORP.    <Polymetallocarbosilane Resin>-   “Tyranno coat VS-100”-   (containing about 49% by weight of polymetallocarbosilane resin),    produced by Ube Industries, Ltd.-   “Tyranno coat VN-100”-   (containing about 50% by weight of polymetallocarbosilane resin and    silicone resin),-   produced by Ube Industries, Ltd.    <Silicone Resin>-   “KR255”-   (containing about 50% by weight of straight silicone resin),    produced by Shin-Etsu Chemical Co., Ltd.-   “TSR116”-   (containing about 50% by weight of straight silicone resin),-   produced by GE Toshiba Silicones,-   “KR3701”-   (containing about 60% by weight of silicone adhesive),-   produced by Shin-Etsu Chemical Co., Ltd.-   “ES-1002T”-   (containing about 50% by weight of epoxy-modified straight silicone    resin),-   produced by Shin-Etsu Chemical Co., Ltd.    <Inorganic Powder>-   “KR-380”-   (rutile type titanium oxide),-   produced by Titan Kogyo K.K.-   “TRNS OXIDE RED AA2005”-   (Fe₂O₃),-   produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd.-   “BI kaolin”-   (kaolin),-   produced by Maruo Calcium Co., Ltd.-   Zinc powder-   (zinc),-   produced by Mizusawa Kagaku Yakuhin K.K.-   “AT-Sn. No. 600”-   (tin),-   produced by YAMAISHIMETALS.CO.LTD.-   “AC-2500”-   (aluminum),-   produced by TOYO ALUMINIUM K.K.-   Note: In addition to the above, commercially available inorganic    powders are used.    <Dispersant>-   “Disparlon DA705”,-   produced by Kusumoto Chemicals, Ltd.    <Heat-Resistant Ink>-   “HP-350A”,-   produced by General Corporation.    <Aluminum Foil Layer>-   Aluminum foil: “1N-30-H-40RT”,-   40 μm thick,-   produced by Nippon Foil Mfg. Co., Ltd.    <Adhering Layer>-   Polyisobutylene resin:-   “Tetrax 4T”,-   produced by Nippon Oil Corporation.    <Release Sheet>-   “PET-50x1SS-4B” (fluoride film),-   produced by Nippa corporation

Rubbing tests were conducted by rubbing an sticking layer or a labelbase layer at a pressure of 0.5 to 1 kg/cm² using 3 to 5 pieces of gauzesoaked in xylene. In the rubbing test, when the layer was removed by 5or 6 rubbings and adhered to the gauze, the layer was defined as ahardened, and when the layer was not removed by 15 rubbings and hadbarely adhered to gauze, the layer was defined as a cured.

EXAMPLE 1 Heat-Resistant Label 1-1

20 parts by weight of Tyranno coat VS-100 as a polymetallocarbosilaneresin, 60 parts by weight of KR-380 as inorganic powder, 0.5 parts byweight of Disparon DA705 as a dispersant, and 5 parts by weight ofxylene as organic solvent were kneaded. Thereafter, the resultantmixture was dispersed at 3000 rpm for 1 hour using a bead milldispersion machine (“LMZ-2”, manufactured by Ashizawa Finetech Ltd.After confirming the mean particle diameter was 5 μm or less by a grindgauge, a dispersion mill base M-1 was obtained.

20 g of KR255 as a silicone resin was added to 85.5 g of the dispersionmill base M-1, and subsequently 5 g of xylene was added thereto,followed by kneading. Further, xylene was added to the resultant mixtureso as to adjust the viscosity to be 25 to 30 seconds/25° C. byviscometer using an I.H.S consistency cup (manufactured by Anest Iwata,to form a coating composition. Subsequently, the coat solution wasapplied to one side of a 40 μm thick aluminum foil using a bar coater sothat the dry film thickness was 15 μm, and dried for 10 minutes at 250°C. using a convection oven (ASSF-114S, manufactured by Isuzu SeisakushoCo., Ltd.), and then allowed to stand at room temperature. Afterconfirming the resultant coating film was cured by the rubbing test, asupport provided with a label base layer was obtained.

In the next process, the coating composition was applied to the otherside of the support (i.e., the sticking layer side) with a bar coater sothat the dry film thickness was 40 pun, dried at 200° C. for 5 minutesusing a convection oven (ASSF-114S, manufactured by Isuzu SeisakushoCo., Ltd.), and then allowed to stand at room temperature. Afterconfirming the resultant coating film was hardened by the rubbing test,the coating film was cut into 5 cm×3 cm pieces, giving heat-resistantlabels.

EXAMPLE 2 TO 14 Heat-Resistant Labels 1-1

Heat-resistant labels were prepared using the components and under thedrying conditions shown in Tables 1 to 3 in the same manner as inExample 1. In Examples 10 to 12, dispersion was conducted at 3000 rpmfor 3 hours, and not 1 hour using a bead mill dispersion machine. InExample 13, a hardened coating film (sticking layer) only was formedonto one side of the support, and no cured coating film (label baselayer) was formed.

COMPARATIVE EXAMPLES 1 TO 3

Labels provided with a sticking layer were obtained using the componentsand under the drying conditions shown in Table 4 in the same manner asin Example 1. TABLE 1 Ex. Ex. Ex. Ex. Ex. 1 2 3 4 5 Composition TYRANNO20 30 30 20 20 of the COAT VS-100 label 1 TYRANNO — — — — base layerCOAT VN-100 KR255 20 30 — — 10 TSR116 — — 30 20 10 KR-380 60 30 30 60 60TRNS OXIDE — — — — — RED AA2005 DA705 0.5 0.5 0.5 0.5 0.5 XYLENE 10 7 1310 10 Drying condition for 250° C. for 10 minutes the label base layerComposition of the same as the label base layer sticking layer Dryingcondition for at 200° C. for 5 minutes the sticking layer

TABLE 2 Ex. Ex. Ex. Ex. Ex. 6 7 8 9 10 Composition TYRANNO — — — — — ofthe COAT label 1 VS-100 base layer TYRANNO 40 40 30 30 30 COAT VN-100KR255 — — 10 10 10 TSR116 — — — 10 10 KR-380 20 60 60 60 — TRNS — — — —60 OXIDE RED AA2005 DA705 0.5 0.5 0.5 0.5 0.5 XYLENE 10 10 10 10 10Drying condition for 250° C. for 10 minutes the label base layerComposition of the same as the label base layer same as sticking layerthe label base layer of Ex. 1 Drying condition 200° C. for 5 minutes forthe sticking layer

TABLE 3 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Composition TYRANNO — — — 20 of theCOAT label 1 VS-100 base layer TYRANNO 60 30 — — COAT VN-100 KR255 20 10— 20 TSR116 20 10 — — KR-380 — 30 — — BI kaolin — — — 60 TRNS OXIDE 6030 — — RED AA2005 DA705 0.5 0.5 — 0.5 XYLENE 10 10 — 10 Drying conditionfor the 250° C. for 10 minutes label base layer Composition of the sameas the same as the same as the same as the sticking layer label baselabel base label base label base layer of Ex. 6 layer of Ex. 10 layer ofEx. 10 layer of Ex. 1 Drying condition for 200° C. for 5 minutes thesticking layer

TABLE 4 Com. Com. Com. Ex. 1 Ex. 2 Ex. 3 Composition TYRANNO COAT — — —of the VS-100 sticking TYRANNO COAT — — — layer VN-100 KR255 60 40 —TSR116 — — 60 KR-380 30 60 30 TRNS OXIDE — — — RED AA2005 DA705 0.5 0.50.5 XYLENE 1 10 13 Drying condition for the 150° C. for 5 minutessticking layer Composition of the label same as the label base layer ofEx. 1 1 base layer Drying condition for the 250° C. for 10 minutes labelbase layer

TEST EXAMPLE 1

The following tests were conducted using the labels obtained in theabove-mentioned Examples 1 to 14 and Comparative Examples 1 to 3. Theresults are shown in Tables 5 and 6. In addition to these test results,it was found that a barcode was clearly printed on the label base layerof Example 14. A label with a barcode printed was attached to a productunder the same conditions as in the label attachment tests 1, 2, and 3,and the printed barcode state was found to be distinct without beingpeeled off by the label attaching machine, and was favorably readout bya barcode reader.

High Temperature Label Attachment Test 1:

Each label was compressed to an aluminum billet at a side with a surfacetemperature of 500° C. at a pressure of 50 g/cm² for 5 seconds using amanually-operated label attaching machine. Thereafter, the aluminumbillet was allowed to cool to room temperature, and was observed forlabel attachment state, appearance and scratch resistance. Theappearance and scratch resistance of the label of Example 13 were notevaluated since it was not provided with a label base layer. The resultsare shown in Table 5.

The label adhesion was evaluated according to the following criteria:

-   A: The label is not peeled off; and-   C: The label is peeled off.

The criteria for evaluating the appearance were as follows:

-   C: The label base layer is partially peeled off the support; and-   A: No change observed.

The scratch resistance was evaluated by scratching the label base layer2 or 3 times at a speed of 5 cm/second using a coin while applying aload of about 500 g to the coin, and the evaluation criteria were asfollows:

-   C: The label base layer crumbled and peeled off the support; and-   A: The label base layer is not scratched or the surface of the layer    is slightly peeled off.    High Temperature Label Attachment Test 2:

Evaluations were conducted in the same manner as in the high temperaturelabel attachment test 1 except that the surface temperature of the labelattaching target (aluminum billet) is 600° C. The results are shown inTable 5.

High Temperature Label Attachment Test 3:

Evaluations were conducted in the same manner as in the high temperaturelabel attachment test 1 except that the surface temperature of the labelattachment target (iron billet) is 660° C. The results are shown inTable 6. TABLE 5 Attachment test 1 Attachment test 2 500° C. 600° C.Adhe- Appear- Scratch Adhe- Appear- Scratch sion ance resistance sionance resistance Ex. 1 A A A A A A Ex. 2 A A A A A A Ex. 3 A A A A A AEx. 4 A A A A A A Ex. 5 A A A A A A Ex. 6 A A A A A A Ex. 7 A A A A A AEx. 8 A A A A A A Ex. 9 A A A A A A Ex. 10 A A A A A A Ex. 11 A A A A AA Ex. 12 A A A A A A Ex. 13 A — — A — — Ex. 14 A A A A A A Com. C C C CC C Ex. 1 Com. C C C C C C Ex. 2 Com. C C C C C C Ex. 3

TABLE 6 Attachment test 3 660° C. Scratch Adhesion Appearance resistanceEx. 1 A A A Ex. 2 A A A Ex. 3 A A A Ex. 4 A A A Ex. 5 A A A Ex. 6 A A AEx. 7 A A A Ex. 8 A A A Ex. 9 A A A Ex. 10 A A A Ex. 11 A A A Ex. 12 A AA Ex. 13 A — — Ex. 14 A A A Com. Ex. 1 C C C Com. Ex. 2 C C C Com. Ex. 3C C C

EXAMPLE 15 Heat-Resistant Label 2

20 parts by weight of Tyranno coat VS-100 as a polymetallocarbosilaneresin, 60 parts by weight of KR-380 as inorganic powder, 0.5 parts byweight of Disparon DA705 as a dispersant, and 5 parts by weight ofxylene as organic solvent were kneaded. Thereafter, the resultantmixture was dispersed at 3000 rpm for 1 hour using a bead milldispersion machine (“LMZ-2”, manufactured by Ajisawa Finetech Ltd. Afterconfirming the mean particle diameter was 5 μm or less by a grind gauge,a dispersion mill base M-1 was obtained.

20 g of KR255 as a silicone resin was added to 85.5 g of the dispersionmill base M-1, and subsequently 5 g of xylene was added thereto,followed by kneading. Further, xylene was added to the resultant mixtureso as to adjust the viscosity to be 25 to 30 seconds/25° C. by viscositymeasurement using an I. H. S consistency cup (manufactured by AnestIwata), to form a coating composition. Subsequently, the coatingcomposition was applied with a bar coater to one side of a stainlesssteel foil 20 μm thick so that the dry film thickness was 15 μm, anddried for 10 minutes at 250° C. using a convection oven (ASSF-114S,manufactured by Isuzu Seisakusho Co., Ltd.), and then allowed to cool toroom temperature. After confirming that the resultant coating film wascured by the rubbing test, a support provided with a label base layerwas obtained.

In the next process, Tetrax 4T was applied as an adhesive with a barcoater to one entire side of an aluminum foil 40 μm thick so that thedry film thickness was 8 μm, and dried at 100° C. for 5 minutes using aconvection oven (ASSF-114S, manufactured by Isuzu Seisakusho Co., Ltd.),and was allowed to cool to room temperature, giving an aluminum foillayer provided with an adhering layer.

The obtained support with the label base layer, and aluminum foil withthe adhering layer, were pasted together. The obtained laminated sheetwas cut into 5 cm×3 cm pieces, giving heat-resistant labels.

EXAMPLES 16 TO 27 Heat-Resistant Labels 2

Heat-resistant labels were obtained using the compositions and under thedrying conditions shown in Tables 7 to 9 in the same manner as inExample 15. In Examples 24 to 26, dispersion using a bead milldispersion machine was conducted at 3000 rpm for 3 hours, and not 1hour. In Example 27, only an aluminum foil was formed onto one side ofthe support with an adhering layer, and a cured coating film (i.e.,label base layer) was not formed. TABLE 7 Ex. Ex. Ex. Ex. Ex. 15 16 1718 19 Composition TYRANNO 20 30 30 20 20 of the COAT label VS-100 baselayer TYRANNO — — — — — COAT VN-100 KR255 20 30 — — 10 TSR116 — — 30 2010 KR-380 60 30 30 60 60 TRNS — — — — — OXIDE RED AA2005 DA705 0.5 0.50.5 0.5 0.5 XYLENE 10 7 13 10 10 Drying condition of 250° C. for 10minutes the label base layer Structure of the adhering layer andaluminum foil adhering layer

TABLE 8 Ex. Ex. Ex. Ex. Ex. 20 21 22 23 24 Composition TYRANNO — — — — —of the COAT label VS-100 base layer TYRANNO 40 40 30 30 30 COAT VN-100KR255 — — 10 10 10 TSR116 — — — 10 10 KR-380 20 60 60 60 — TRNS — — — —60 OXIDE RED AA2005 DA705 0.5 0.5 0.5 0.5 0.5 XYLENE 10 10 10 10 10Drying condition of 250° C. for 10 minutes the label base layerStructure of the adhering layer and aluminum foil adhering layer

TABLE 9 Ex. 25 Ex. 26 Ex. 27 Composition TYRANNO — — — of the label COATbase layer VS-100 TYRANNO 60 30 — COAT VN-100 KR255 20 10 — TSR116 20 10— KR-380 — 30 — TRNS OXIDE 60 30 — RED AA2005 DA705 0.5 0.5 — XYLENE 1010 — Drying condition of the 250° C. for 10 minutes — label base layerStructure of the adhering adhering layer and aluminum foil layer

EXAMPLES 28 TO 39 Heat-Resistant Labels 2

Heat-resistant labels were obtained in the same manner as in Example 15except that the adhesive was applied in stripe-like patterns to one sideof the aluminum foil using the compositions and under the dry conditionsshown in Tables 10 to 12. The adhesive application method was asfollows.

Adhesive applied areas of 5 mm width and non-adhesive applied areas of10 mm width were sequentially provided on one side of the aluminum foilusing a barcoater with the adhesive being applied in stripes at an angleof 45° in a spiral manner.

In Examples 36 to 38, dispersion using a bead mill dispersion machinewas conducted at 3000 rpm for 3 hours, and not 1 hour. In Example 39,only an aluminum foil was formed onto one side of the support with anadhering layer, and a cured coating film (i.e., label base layer) wasnot formed. TABLE 10 Ex. Ex. Ex. Ex. 28 29 30 31 Composition TYRANNO 3030 20 20 of the COAT label VS-100 base layer TYRANNO — — — — COAT VN-100KR255 30 — — 10 TSR116 — 30 20 10 KR-380 30 30 60 60 TRNS OXIDE — — — —RED AA2005 DA705 0.5 0.5 0.5 0.5 XYLENE 7 13 10 10 Drying condition of250° C. for 10 minutes the label base layer Structure of the adheringlayer and aluminum foil adhering layer

TABLE 11 Ex. Ex. Ex. Ex. Ex. 32 33 34 35 36 Composition TYRANNO — — — —— of the COAT label VS-100 base layer TYRANNO 40 40 30 30 30 COAT VN-100KR255 — — 10 10 10 TSR116 — — — 10 10 KR-380 20 60 60 60 — TRNS — — — —60 OXIDE RED AA2005 DA705 0.5 0.5 0.5 0.5 0.5 XYLENE 10 10 10 10 10Drying condition of 250° C. for 10 minutes the label base layerStructure of the adhering layer and aluminum foil adhering layer

TABLE 12 Ex. 37 Ex. 38 Ex. 39 Composition TYRANNO COAT — — — of thelabel VS-100 base layer TYRANNO COAT 60 30 — VN-100 KR255 20 10 — TSR11620 10 −s KR-380 — 30 — TRNS OXIDE 60 30 — RED AA2005 DA705 0.5 0.5 —XYLENE 10 10 — Drying condition of the 250° C. for 10 minutes label baselayer Structure of the adhering adhering layer and aluminum foil layer

TEST EXAMPLE 2

The following tests were conducted using the labels obtained in theabove Examples 15 to 39 and Comparative Examples 1 to 3.

High Temperature Label Attachment Test 4:

Testing was conducted in the same manner as in the high temperaturelabel attachment test 1 except that the surface temperature of the labelattachment target (iron billet) was 680° C. The appearance was evaluatedand-those-labels showing slight cracking were rated as “B”. The resultsare shown in Table 13.

High Temperature Label Attachment Test 5:

Testing was conducted in the same manner as in the high temperaturelabel attachment test 1 except that the surface temperature of the labelattachment target (iron billet) was 700° C. The label of Example 1 wasnot evaluated. The results are shown in Table 13.

High Temperature Label Attachment Test 6:

Testing was conducted in the same manner as in the high temperaturelabel attachment test 1 except that the surface temperature of the labelattachment target (iron billet) was 1000° C. The label of Example 1 wasnot evaluated. The results are shown in Table 14. TABLE 13 Attachmenttest 4 Attachment test 5 680° C. 700° C. Adhe- Appear- Scratch Adhe-Appear- Scratch sion ance resistance sion ance resistance Ex. 1 A B A —— — Ex. 15 A A A A A A Ex. 16 A A A A A A Ex. 17 A A A A A A Ex. 18 A AA A A A Ex. 19 A A A A A A Ex. 20 A A A A A A Ex. 21 A A A A A A Ex. 22A A A A A A Ex. 23 A A A A A A Ex. 24 A A A A A A Ex. 25 A A A A A A Ex.26 A A A A A A Ex. 27 A — — A — — Ex. 28 A A A A A A Ex. 29 A A A A A AEx. 30 A A A A A A Ex. 31 A A A A A A Ex. 32 A A A A A A Ex. 33 A A A AA A Ex. 34 A A A A A A Ex. 35 A A A A A A Ex. 36 A A A A A A Ex. 37 A AA A A A Ex. 38 A A A A A A Ex. 39 A — — A — — Com. C C C C C C Ex. 1Com. C C C C C C Ex. 2 Com. C C C C C C Ex. 3

TABLE 14 Attachment test 6 1000° C. Scratch Adhesion Appearanceresistance Ex. 15 A A A Ex. 16 A A A Ex. 17 A A A Ex. 18 A A A Ex. 19 AA A Ex. 20 A A A Ex. 21 A A A Ex. 22 A A A Ex. 23 A A A Ex. 24 A A A Ex.25 A A A Ex. 26 A A A Ex. 27 A — — Ex. 28 A A A Ex. 29 A A A Ex. 30 A AA Ex. 31 A A A Ex. 32 A A A Ex. 33 A A A Ex. 34 A A A Ex. 35 A A A Ex.36 A A A Ex. 37 A A A Ex. 38 A A A Ex. 39 A — — Com. Ex. 1 C C C Com.Ex. 2 C C C Com. Ex. 3 C C C

EXAMPLES 40 AND 41 (HEAT-RESISTANT LABELS 1-1) AND COMPARATIVE EXAMPLES4 AND 5

Heat-resistant labels were prepared in a similar manner as in Example 1except that the thickness after drying of the coating film of theadhering layers was 30 μm, and drying conditions were: room temperaturefor 10 minutes (Comparative Example 4), 100° C. for 5 minutes 10(Example 40), 200° C. for 5 minutes (Example 41), and 300° C. for 5minutes (Comparative Example 5).

Each label was placed on the top surface of an aluminum billet having asurface temperature of 500° C. and pressed thereto at a pressure of 50g/cm² for 5 seconds. The aluminumbillet after pressing was cooled toroom temperature. The ignition, appearance and adhesion of each labelwere examined.

As for the ignition of the labels, those that did not ignite were graded“A” and those that ignited were graded “C”. As for the appearance of thelabels, those that did not scorch were graded “A” and those thatscorched were graded “C”. As for the adhesion of the labels, those thatsecurely adhered to the billet without loosening were graded “A” andthose that loosened or peeled off from the billet were graded “C”. Theresults-.are presented in Table 15. TABLE 15 Thickness Drying of CoatingAppear- condition film Ignition ance Adhesion Comp. Room 30 μm C C A Ex.4 temperature for 10 min Ex. 40 100° C. 30 μm A A A for 5 min Ex. 41200° C. 30 μm A A A for 5 min Comp. 300° C. 30 μm A A C Ex. 5 for 5 min

The label of Comparative Example 4 having a large solvent contentignited at 500° C. The label of Comparative Example 5 whose stickinglayer was comprised of a coating film that had been cured rather thanhardened did not adhere.

EXAMPLES 42 Heat-Resistant Label 1-2

A label base layer was created in a similar manner as in Example 1 onone side of an aluminum foil having a thickness of 40 μm.

20 parts by weight of KR3701 as a silicone resin, 36 parts by weight ofzinc powder as an inorganic powder, 0.3 parts by weight of DisparonDA705 as a dispersant, and 20 parts by weight of xylene as an organicsolvent were kneaded. Thereafter, the resultant mixture was dispersedusing a bead mill dispersion machine as described previously at 3000 rpmfor 1 hour. After confirming the mean particle diameter was 5 μm or lessby a grind gauge, a dispersion mill base M-2 was obtained. 4 g of KR3701was added to 76.3 g of the dispersion mill base M-2, and subsequently 10g of xylene was added thereto, followed by kneading. Xylene was furtheradded to the resultant mixture so as to adjust the viscosity to be 55 to60 seconds/25° C. by a viscometer using an I•H•S consistency cup, toform a coating composition. Subsequently, the coating composition wasapplied to the other side of the support using a bar coater such thatthe dry film thickness was 40 μm, and dried at 200° C. for 5 minutesusing a convection oven (ASSF-114S, manufactured by Isuzu SeisakushoCo., Ltd.) to remove the solvent contained in the coating film, and thenallowed to stand at room temperature. The surface of the sticking layerof the resulting sheet was laminated with a release sheet coated withfluoro resin, and a 5 cm×3 cm piece was cut from the laminated sheet,thereby giving a heat-resistant label. When this label was stuck to anarticle, the release sheet was removed and then-the surface of thesticking layer was attached to an article.

EXAMPLES 43 TO 47 Heat-Resistant Labels 1-2

Heat-resistant labels were prepared using the compositions presented inTable 16 in a similar manner as in Example 42. TABLE 16 Ex. Ex. Ex. Ex.Ex. Ex. 42 43 44 45 46 47 Composition of same as the label base layer ofEx. 1 label base layer Drying condition 250° C. for 10 minutes for labelbase layer Composition KR3701 24 40 24 40 24 40 of sticking Zinc 36 36 —— — — layer powder Tin — — 36 36 — — powder Al — — — — 36 36 powderDA705 0.3 0.3 0.3 0.3 0.3 0.3 Xylene 30 40 30 40 30 40 Drying condition200° C. for 5 minutes for sticking layer

EXAMPLES 48 TO 53 Heat-Resistant Labels 1-2

Heat-resistant labels were prepared using the compositions shown inTable 17 in a similar manner as in Example 42 except that KR255 was usedas a silicone resin. No release sheet was used since it was unnecessary.TABLE 17 Ex. Ex. Ex. Ex. Ex. Ex. 48 49 50 51 52 53 Composition of sameas the label base layer of Ex. 1 label base layer Drying condition 250°C. for 10 minutes for label base layer Composition KR255 24 40 24 40 2440 of sticking Zinc 30 30 — — — — layer powder Tin — — 30 30 — — powderAl — — — — 30 30 powder DA705 0.3 0.3 0.3 0.3 0.3 0.3 Xylene 30 40 30 4030 40 Drying condition 200° C. for 5 minutes for sticking layer

EXAMPLES 54 TO 59 Heat-Resistant-Labels 1-2

Heat-resistant labels were prepared using the compositions shown inTable 18 in a similar manner as in Example 42 except that ES-1002T wasused as a silicone resin. No release sheet was used since it wasunnecessary. TABLE 18 Ex. Ex. Ex. Ex. Ex. Ex. 54 55 56 57 58 59Composition of same as the label base layer of Ex. 1 label base layerDrying condition 250° C. for 10 minutes for label base layer CompositionES-1002T 24 40 24 40 24 40 of sticking Zinc 30 30 — — — — layer powderTin — — 30 30 — — powder Al — — — — 30 30 powder DA705 0.3 0.3 0.3 0.30.3 0.3 Xylene 8 12 8 12 8 12 Drying condition 200° C. for 5 minutes forsticking layer

COMPARATIVE EXAMPLES 6 TO 8

Heat-resistant labels were prepared using the compositions shown inTable 19 in a similar manner as in Example 42 except that no inorganicpowder was used. A release sheet was used only for the label ofComparative Example 6 in which silicone adhesive KR3701 was used. TABLE19 Comp. Ex. 6 Comp. Ex. 7 Comp. Ex. 8 Composition of label same as thelabel base layer of Ex. 1 base layer Drying condition for 250° C. for 10minutes label base layer Composition KR3701 50 — — of sticking KR255 —50 — layer ES-1002T — — 50 DA705 — — — Xylene 10 10 10 Drying conditionfor 200° C. for 5 minutes sticking layer

EXAMPLES 9 TO 17

Heat-resistant labels were prepared using the compositions shown inTables 20 and 21 in a similar manner as in Example 42 except thatinorganic powders other than powders of zinc, tin and aluminum wereused. TABLE 20 Comp. Comp. Comp. Comp. Comp. Ex. 9 Ex. 10 Ex. 11 Ex. 12Ex. 13 Composition of same as the label base layer of Ex. 1 label baselayer Drying condition 250° C. for 10 minutes for label base layerComposition KR3701 24 24 24 24 24 of sticking Thallium 36 — — — — layerpowder Kaolin — 36 — — — powder Bismuth — — 36 — — powder Iron — — — 36— powder Selenium — — — — 36 powder DA705 0.3 0.3 0.3 0.3 0.3 Xylene 3030 30 30 30 Drying condition 200° C. for 5 minutes for sticking layer

TABLE 21 Comp. Comp. Comp. Comp. Ex. 14 Ex. 15 Ex. 16 Ex. 17 Compositionof same as the label base layer of Ex. 1 label base layer Dryingcondition 250° C. for 10 minutes for label base layer Composition KR370124 24 24 24 of sticking Tellurium 36 — — — layer powder Indium — 36 — —powder Magnesium — — 36 — powder Antimony — — — 36 powder DA705 0.3 0.30.3 0.3 Xylene 30 30 30 30 Drying condition 200° C. for 5 minutes forsticking layer

TEST EXAMPLE3

High-temperature label attachment tests 1 to 3 were performed using thelabels obtained in Examples 42 to 59 and Comparative Examples 6 to 17 ina similar manner as in Test Example 1 except that the labels were leftto stand for4 hours at the same temperature as their application. Theresults are presented in Tables 22 and 23. TABLE 22 Attachment test 1Attachment test 2 500° C. 600° C. Adhe- Appear- Scratch Adhe- Appear-Scratch sion ance resistance sion ance resistance Ex. 42 A A A A A A Ex.43 A A A A A A Ex. 44 A A A A A A Ex. 45 A A A A A A Ex. 46 A A A A A AEx. 47 A A A A A A Ex. 48 A A A A A A Ex. 49 A A A A A A Ex. 50 A A A AA A Ex. 51 A A A A A A Ex. 52 A A A A A A Ex. 53 A A A A A A Ex. 54 A AA A A A Ex. 56 A A A A A A Ex. 57 A A A A A A Ex. 58 A A A A A A Ex. 59A A A A A A Comp. C C A C C A Ex. 4 Comp. C C A C C A Ex. 5 Comp. C C AC C A Ex. 6 Comp. C C A C C A Ex. 7 Comp. C C A C C A Ex. 8 Comp. C C AC C A Ex. 9 Comp. C C A C C A Ex. 10 Comp. C C A C C A Ex. 11 Comp. C CA C C A Ex. 12 Comp. C C A C C A Ex. 13 Comp. C C A C C A Ex. 14 Comp. CC A C C A Ex. 15 Comp. C C A C C A Ex. 16 Comp. C C A C C A Ex. 17

TABLE 23 Attachment test 3 660° C. Scratch Adhesion Appearanceresistance Ex. 42 A A A Ex. 43 A A A Ex. 44 A A A Ex. 45 A A A Ex. 46 AA A Ex. 47 A A A Ex. 48 A A A Ex. 49 A A A Ex. 50 A A A Ex. 51 A A A Ex.52 A A A Ex. 53 A A A Ex. 54 A A A Ex. 56 A A A Ex. 57 A A A Ex. 58 A AA Ex. 59 A A A Comp. Ex. 4 C C A Comp. Ex. 5 C C A Comp. Ex. 6 C C AComp. Ex. 7 C C A Comp. Ex. 8 C C A Comp. Ex. 9 C C A Comp. Ex. 10 C C AComp. Ex. 11 C C A Comp. Ex. 12 C C A Comp. Ex. 13 C C A Comp. Ex. 14 CC A Comp. Ex. 15 C C A Comp. Ex. 16 C C A Comp. Ex. 17 C C A

INDUSTRIAL APPLICABILITY

The label of the invention is heat-resistant, and thus can be attachedto a heat-resistant product having high temperatures during ahigh-temperature treatment or immediately after the treatment.Therefore, product management using the heat-resistant label withbarcodes, etc. can be conducted at an earlier stage. Moreover, thepresent invention can eliminate the necessity of a cooling period,cooling energy, and a cooling place which are required for cooling theheat-resistant products such as metal products, etc. to room temperatureso as to attach conventional labels thereon. For example, in productionof a stainless steel billet, the heat-resistant label 2 can be attachedto a stainless steel billet having a temperature of about 1100° C.During production of an aluminum billet, the heat-resistant label 1 canbe attached to the aluminum billet having a temperature of about 650° C.immediately after manufacturing.

The label of the present invention can be used for controllingdistribution and sales as in conventional bar-code labels, etc., unlessthe label is not taken off after attachment. In the invention, a productrepresents not only commercial products after manufacturing but also rawmaterials, intermediate products, etc. during the production process.

1. A composition for a heat-resistant label comprising a silicone resin(A), at least one member selected from the group consisting of apolymetallocarbosilane resin, zinc powder, tin powder and aluminumpowder (B), and a solvent (C).
 2. A composition for a heat-resistantlabel according to claim 1, comprising a silicone resin (A), apolymetallocarbosilane resin (B-1), and a solvent (C).
 3. A compositionfor a heat-resistant label according to claim 1, wherein the weightratio of the silicone resin (A): the polymetallocarbosilane resin (B-1)is about 1:9 to about 9:1.
 4. A composition for a heat-resistant labelaccording to claim 1, wherein the weight ration of the silicone resin(A): the polymetallocarbosilane resin (B-1) is about 7:3 to about 2:8.5. A composition for a heat-resistant label according to claim 1,wherein the silicone resin (A) has a weight-average molecular weight ofabout 1000 to about
 500000. 6. A composition for a heat-resistant labelaccording to claim 1 further comprising an inorganic filler (D).
 7. Acomposition for a heat-resistant label according to claim 1 comprising asilicone resin (A), at least one powder selected from the groupconsisting of zinc powder, tin powder, and aluminum powder (B-2), and asolvent (C).
 8. A composition for a heat-resistant label according toclaim 1, wherein the weight ratio of the silicone resin (A): the atleast one powder selected from the group consisting of zinc powder, tinpowder and aluminum powder (B-2) is about 1:5 to about 10:1.
 9. Acomposition for a heat-resistant label according to claim 1 comprising asilicone resin (A), a polymetallocarbosilane resin (B-1), at least onepowder selected from the group consisting of zinc powder, tin powder,and aluminum powder (B-2), and a solvent (C).
 10. A composition for aheat-resistant label according to claim 1, wherein thepolymetallocarbosilane resin (B-1) is at least one member selected fromthe group consisting of polytitanocarbosilane resins andpolyzirconocarbosilane resins.
 11. A composition for a heat-resistantlabel according to claim 1, wherein the polymetallocarbosilane resin(B-i) has a weight-average molecular weight of about 500 to about 10000.12. A heat-resistant label having a sticking layer on a sticking side ofa support, the sticking layer comprising a hardened coating filmcomprising a silicone resin (A) and at least one member selected fromthe group consisting of a polymetallocarbosilane resin, zinc powder, tinpowder, and aluminum powder (B).
 13. A heat-resistant label according toclaim 12, wherein the hardened coating film is obtained by applying tothe support a composition of claim 1 and evaporating off the solventcontained in the composition.
 14. A heat-resistant label according toclaim 12, wherein the hardened coating film comprises a silicone resin(A) and a polymetallocarbosilane resin (B-1).
 15. A heat-resistant labelaccording to claim 12, wherein the hardened coating film comprises asilicone resin (A) and at least one high-temperature-adhering inorganicpowder selected from the group consisting of zinc powder, tin powder,and aluminum powder (B-2).
 16. A heat-resistant label according to claim12, wherein the hardened coating film comprises a silicone resin (A), apolymetallocarbosilane resin (B-1), and at least onehigh-temperature-adhering inorganic powder selected from the groupconsisting of zinc powder, tin powder, and aluminum powder (B-2).
 17. Aheat-resistant label according to claim 12, wherein the sticking layerhas a thickness of about 5 μm to about 100 μm.
 18. A heat-resistantlabel according to claim 12, wherein the support ha a thickness of about5 μm to about 100 μm.
 19. A heat-resistant label according to claim 12,wherein the support is an aluminum foil, stainless steel foil, or copperfoil.
 20. A heat-resistant label according to claim 12 having aheat-resistant base layer on a display side of the support.
 21. Aheat-resistant label according to claim 20, wherein the label base layeris a cured coating film comprising a silicone resin (A) and apolymetallocarbosilane resin (B-1).
 22. A heat-resistant label accordingto claim 20, wherein the label base layer is a cured coating filmobtained by applying to the support a composition according to claim 2and heating the composition.
 23. A heat-resistant label according toclaim 20, wherein the label base layer has a thickness of about 0.5 μmto about 100 μm.
 24. A heat-resistant label according to claim 20 havingan identification part on the label base layer.
 25. An article to whicha heat-resistant label of claim 12 is attached through a cured stickinglayer.
 26. A method for producing a heat-resistant label, the methodcomprising the steps of: applying a composition of claim 1 to a stickingside of a support; and drying the applied composition to form a hardenedcoating film.
 27. A production method according to claim 26, wherein theapplied composition is dried at about 50° C. to about 240° C.
 28. Aproduction method according to claim 26, comprising, prior to the stepof applying a composition of claim 1 to the sticking side of a support,the steps of: applying a composition for a heat-resistant label baselayer to a display side of a support; and drying the applied compositionto form a cured coating film.
 29. A production method according to claim28, wherein the composition for a label base layer is a composition ofclaim
 2. 30. A method for producing an article with a heat-resistantlabel attached, the method comprising the step of attaching aheat-resistant label of claim 12 to an article at about 300° C. to about670° C.
 31. A heat-resistant label comprising a support and a metal foillayer comprising at least one member selected from the group consistingof an aluminum foil, aluminum-alloy foil, tin foil, and tin-alloy foil.32. A heat-resistant label according to claim 31, wherein the metal foillayer is laminated on the support through an adhering layer.
 33. Aheat-resistant label according to claim 31, wherein the metal foil layerhas a thickness of 5 μm to 100 μm.
 34. A heat-resistant label accordingto claim 31, wherein the support is a stainless steel foil, copper foil,or iron foil.
 35. A heat-resistant label according to claim 31,comprising a heat-resistant label base layer on a display side of thesupport.
 36. A heat-resistant label according to claim 35, wherein thelabel base layer has a thickness of about 0.5 μm to about 100 μm.
 37. Aheat-resistant label according to claim 35, wherein the label base layeris a cured coating film obtained by crosslinking the resins of acomposition of claim
 2. 38. A heat-resistant label according to claim 35comprising an identification part on the label base layer.
 39. Anarticle to which a heat-resistant label of claim 31 is attached.
 40. Amethod for producing an article with a heat-resistant label attached,The method comprising the step of attaching a heat-resistant label ofclaim 31 to an article at about 670° C. to about 1100° C.